Cathode

Abstract

A cathode material suitable for aluminum-ion batteries is disclosed, which comprises a main group element nitride and an oxide of a main group element or an oxide of an element of Groups 1 to 13. The nitride is preferably a two-dimensional layered material. Preferably, the ratio of the main group element nitride to the oxide is between 5:95 and 95:5 (by weight).

Description

[Technical Field]

[0001] The present invention relates to an improved cathode for an aluminum-ion battery, an aluminum-ion battery comprising the improved cathode, and a method for making a cathode for an aluminum-ion battery. [Background technology]

[0002] Batteries are an important source of stored electrical energy and are widely used in many different types of devices and applications.

[0003] The performance of a battery is highly dependent on many factors, including the physicochemical properties of the battery's electrode materials and electrolyte, which affect battery performance by reducing the battery voltage, coulombic efficiency, the rate capability (maximum charge / discharge rate) of the cell, and the stability of the cell.

[0004] Many different types of batteries are in use, including lead acid, nickel and cadmium-based, and ion batteries. Common to all of these battery types is the presence of a cathode, an anode, and an electrolyte, which can be connected to form an electrical circuit and used to provide a source of energy for a device.

[0005] In recent years, there has been growing interest in ion batteries for use in commercial applications due to the benefits that such batteries can offer. Currently, lithium-ion batteries (LIBs) offer higher charge density, lower self-discharge, lower memory effect, shorter charging times, and less maintenance than other rechargeable batteries such as nickel-cadmium (NiCd) and nickel-metal hydride (NiMH).

[0006] LIBs have found widespread applications in devices such as electric vehicles, mobile phones, and other electronic devices. However, they have not yet been widely adopted for large-scale grid energy storage. The LIB industry uses 42% of the world's production of cobalt, an essential metal for lithium-ion cells. Lithium metal is highly reactive, and transporting the raw material requires special care to prevent physical or electrical harm. Despite substantial cost reductions in recent years, LIBs are still substantially more expensive than other batteries. Furthermore, LIBs can be subject to thermal runaway. During thermal runaway, the electrolyte heats up during discharge, leading to undesirable exothermic reactions. Excess heat generated within the battery cell can then lead to electrolyte leakage, gas leakage, and / or explosion. LIBs can also form metallic lithium dendrites, which can puncture or damage the battery separator and cause thermal runaway. LIBs also often utilize highly flammable electrolytes, which increases their flammability.

[0007] Lead-acid batteries are another common type of battery and use lead dioxide as the cathode material. Lead-acid batteries are an electrical energy storage system commonly used in automobiles, industrial power plants, trucks, mining vehicles, stationary applications, emergency use, and backup power sources. However, lead-acid batteries pose a risk of fire, explosion, and electric shock. They require a long charging time and can self-discharge after extended periods of inactivity. Despite their widespread use, lead-acid batteries present numerous challenges, including hydrogen and oxygen gas generation, sulfuric acid leakage, battery sulfation (leading to reduced electrical efficiency and cell life), freezing of the battery at low discharge levels, loss of active material from the electrodes, and damage to the electrodes. Furthermore, lead is a heavy metal and is toxic to humans and the environment.

[0008] Nickel-based batteries, such as NiCd and NiMH batteries, use nickel oxyhydroxide (NiOOH) as the cathode material. NiMH batteries are used in hybrid electric vehicles and military communications. However, while NiMH batteries have good cycle life, long shelf life, and can operate over a wide temperature range, the high manufacturing costs of the metal hydride alloy make this type of battery extremely expensive. NiCd batteries offer good performance under harsh conditions and can withstand deep discharge for extended periods. However, the cost of the material is high. Furthermore, cadmium is highly toxic to the environment, and disposal of the batteries at the end of their life is cumbersome. This has led to a decrease in their use (or even a ban) in some regions, such as Europe.

[0009] In contrast, rechargeable aluminum-ion batteries (AIBs) offer a promising alternative to lithium-ion batteries. Aluminum is a trivalent metal with three valence electrons in its outer shell. The trivalency of aluminum allows aluminum-ion batteries to have a higher (theoretical) energy density (more energy per unit volume, 8100 Wh / kg) compared to elements with fewer valence electrons, such as lithium, sodium, potassium, and calcium. The volume of aluminum (4 to 7 times larger than that of lithium and sodium, respectively) offers the potential to dramatically increase the energy density of batteries.

[0010] Additionally, aluminum-ion batteries are safer to handle than the other ion batteries mentioned above. Their electrolytes are non-flammable or much less flammable than the electrolytes in LIBs. They may also have a reduced environmental impact because the battery's main component, aluminum, is more easily recyclable than other ion batteries. They offer ease of handling in the ambient environment, which may provide safety advantages compared to other metal-ion batteries. They are also cheaper to manufacture than other ion batteries, and the base materials used are more abundant.

[0011] Cathode materials for rechargeable aluminum-ion batteries have suffered from a number of inherent problems, including low discharge potential, an unstable discharge voltage plateau (meaning the battery fails to recognize a critical voltage), low electrochemical reversibility (leading to low coulombic efficiency), limited cycle life, and structural degradation of the cathode (leading to low and unstable discharge capacity, which results in a rapid decline after a small number of cycles).

[0012] Because cathode materials are specific to each battery type, a material that works well in one battery type is unlikely to provide similar performance in an aluminum-ion battery. For example, a cathode for a lithium-ion battery may not provide equivalent performance in an aluminum-ion battery. Furthermore, a material used in an anode may not be used as a cathode due to the material's physical properties, which are required to function as an anode or cathode, respectively. Summary of the Invention [Problem to be solved by the invention]

[0013] It is therefore an object of the present invention to provide a cathode for use in aluminum-ion batteries that overcomes the shortcomings of the prior art, or at least provides the public with a useful choice.

[0014] Alternatively, it is an object of the present invention to provide an aluminum-ion battery having a cathode that overcomes some of the drawbacks of the prior art, or at least provides the public with a useful choice. [Means for solving the problem]

[0015] One aspect of the present invention is a cathode for an aluminum ion battery, the cathode comprising an oxide of boron and boron nitride, wherein the ratio of the oxide of boron to the boron nitride is between 5:95 and 95:5 (by weight).

[0016] One aspect of the present invention is an aluminum-ion battery cell including a cathode, wherein the cathode includes an oxide of boron and boron nitride, and the ratio of the oxide of boron to the boron nitride is between 5:95 and 95:5 (by weight).

[0017] One aspect of the present invention is the use of a combination of an oxide of boron and boron nitride in the manufacture of a cathode for an aluminum-ion battery cell, wherein the ratio of the oxide of boron to the boron nitride is between 5:95 and 95:5 (by weight).

[0018] One aspect of the present invention is a cathode for an aluminum ion battery, the cathode comprising a main group element nitride and an oxide of an element of Groups 1 to 13.

[0019] One aspect of the invention is a cathode for an aluminum-ion battery, the cathode comprising a main group element nitride and a main group element oxide.

[0020] One aspect of the present invention is the use of a combination of a main group element nitride and an oxide of a Group 1-13 element in the manufacture of a cathode for an aluminum-ion battery cell, wherein the ratio of the oxide of the Group 1-13 element to the main group element nitride is between 5:95 and 95:5 (by weight).

[0021] One aspect of the invention is the use of a combination of a main group element nitride and a main group element oxide in the manufacture of a cathode for an aluminum-ion battery cell, wherein the ratio of the main group element oxide to the main group element nitride is between 5:95 and 95:5 (by weight). [Brief explanation of the drawings]

[0022] [Figure 1]FIG. 1 is a representative schematic diagram of an aluminum-ion cell containing an AlCl / imidazolium chloride ionic liquid electrolyte according to one embodiment of the present invention, illustrating electron flow during charge and discharge cycles of the battery. [Figure 2] 1 shows a schematic representation of the laboratory model, showing the arrangement of electrodes inside the cell. [Figure 3] Charge / discharge curves at 50 mA / g for the 1st cycle (□), 2nd cycle (△), 10th cycle (◇), and 20th cycle (☆) for an aluminum-ion cell containing a cathode with a 1:1 ratio (by weight) of B2O3 and hexagonal boron nitride are shown. [Figure 4] For aluminum-ion cells containing cathodes with a 1:1 ratio (by weight) of B2O3 and hexagonal boron nitride, at current densities of 50 mA / g (□), 500 mA / g (◯), 900 mA / g (△), 1000 mA / g (◇), 1500 mA / g (☆), and at 50 mA / g for 100 cycles.

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[0023] [Cathode] In one aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a main group element nitride.

[0024] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of a Group 13 element.

[0025] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of boron.

[0026] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of carbon.

[0027] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, said cathode material comprising a nitride of silicon.

[0028] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of aluminum.

[0029] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, said cathode material comprising a nitride of lithium.

[0030] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, said cathode material comprising an oxide of boron.

[0031] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided that includes a main group element nitride and a main group element chalcogenide.

[0032] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, comprising a main group element nitride and a chalcogenide of an element from Groups 1-13 of the periodic table.

[0033] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a main group element nitride and a group 13 element chalcogenide.

[0034] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a main group element nitride and a chalcogenide of boron.

[0035] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided that includes a main group element nitride and a main group element oxide.

[0036] In another aspect of the present invention, there is provided a cathode material for an aluminum-ion battery comprising a main group element nitride and an oxide of a Group 1-13 element.

[0037] In one example, the oxide of an element of Groups 1 to 13 may be selected from oxides of transition metal elements, and specific examples of transition metal oxides include oxides of titanium and manganese.

[0038] In one example, the main group element nitride may be selected from nitrides of boron, carbon, aluminum, and silicon.

[0039] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a main group element nitride and an oxide of a group 13 element.

[0040] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a main group element nitride and an oxide of boron.

[0041] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of a Group 13 element and a chalcogenide of a main group element.

[0042] In another aspect of the present invention, there is provided a cathode material for an aluminum-ion battery, the cathode material comprising a nitride of a Group 13 element and a chalcogenide of an element of Groups 1 to 13 of the periodic table.

[0043] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of a Group 13 element and a chalcogenide of a Group 13 element.

[0044] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of a Group 13 element and a chalcogenide of boron.

[0045] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of a Group 13 element and an oxide of a main group element.

[0046] In another aspect of the present invention, there is provided a cathode material for an aluminum-ion battery, the cathode material comprising a nitride of a Group 13 element and an oxide of an element of Groups 1 to 13 of the periodic table.

[0047] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of a Group 13 element and an oxide of a Group 13 element.

[0048] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of a Group 13 element and an oxide of boron.

[0049] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of boron and a chalcogenide of a main group element.

[0050] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of boron and a chalcogenide of an element of Groups 1 to 13 of the periodic table.

[0051] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of boron and a chalcogenide of a Group 13 element.

[0052] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of boron and a chalcogenide of boron.

[0053] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of boron and an oxide of a main group element.

[0054] In another aspect of the present invention, there is provided a cathode material for an aluminum-ion battery, the cathode material comprising a nitride of boron and an oxide of an element of Groups 1 to 13 of the periodic table.

[0055] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of boron and an oxide of a Group 13 element.

[0056] In another aspect of the present invention, a cathode material for an aluminum-ion battery is provided, the cathode material comprising a nitride of boron and an oxide of boron.

[0057] In one example, the main group element nitride is selected from the group including carbon nitride, lithium nitride, aluminum nitride, boron nitride, silicon nitride, gallium nitride, and indium nitride. Preferred main group element nitrides are selected from the group including carbon nitride, boron nitride, silicon nitride, and aluminum nitride.

[0058] In one example, the chalcogenides of Groups 1 to 13 elements may be selected from alkali metal chalcogenides, alkaline earth metal chalcogenides, transition metal (Groups 3 to 12) chalcogenides, and Group 13 element chalcogenides. The alkali metal chalcogenides may be selected from chalcogenides of lithium, sodium, potassium, and rubidium. The alkaline earth metal chalcogenides may be selected from chalcogenides of beryllium, magnesium, calcium, strontium, and barium. The transition metal chalcogenides may be selected from chalcogenides of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, and mercury. Preferably, the transition metal chalcogenides are selected from chalcogenides of titanium, manganese, vanadium, iron, nickel, zinc, molybdenum, and tantalum. The Group 13 chalcogenides may be selected from oxides of boron, aluminum, gallium, indium, and thallium.

[0059] In one example, the chalcogenide of a Group 1 to 13 element may be selected from oxides of Group 1 to 13 elements, including oxides of transition metal elements, such as oxides of titanium and manganese.

[0060] In one example, the main group element chalcogenide is selected from main group element oxides. In one example, the main group element chalcogenide is selected from boron chalcogenides. In a particular example, the main group element chalcogenide is selected from boron oxides. In a more particular example, the boron oxide is boric anhydride (BO).

[0061] In one example, the main group element nitride may include a morphology selected from a 2D layered material, a crystalline material, a nanoparticle, a quantum dot, a nanowire, a nanosheet, a nanorod, a microparticle sheet, and a flower. Such morphologies will be known to those skilled in the art. In one example, the morphology is a 2D layered material. In one example, the main group element nitride is a 2D layered material of carbon nitride, silicon nitride, aluminum nitride, and boron nitride. In a particular example, the main group element nitride is a hexagonal form of boron nitride.

[0062] Alternatively, when the nitride is boron nitride, the boron nitride may be in any polymorph, such as diamond-like cubic (zinc blende structure), wurtzite boron nitride, and hexagonal boron nitride.

[0063] In examples where the cathode material includes a main group element nitride and a Group 1-13 element chalcogenide, the weight ratio of the chalcogenide to the nitride in the cathode material may be between 5:95 and 95:5, between 10:90 and 90:10, between 20:80 and 80:20, between 30:70 and 70:30, between 40:60 and 60:40, or between 45:55 and 55:45. In particular examples, the ratio is about 50:50. In one example, the proportion of chalcogenide is at least 5% by weight of the active material in the cathode. In one example, the proportion of nitride is at least 5% by weight of the active material in the cathode.

[0064] In examples where the cathode material includes an oxide of a Group 1-13 element and a main group element nitride, the weight ratio of the oxide to the nitride in the cathode material may be between 5:95 and 95:5, between 10:90 and 90:10, between 20:80 and 80:20, between 30:70 and 70:30, between 40:60 and 60:40, or between 45:55 and 55:45. In particular examples, the ratio is about 50:50. In one example, the proportion of oxide is at least 5% by weight of the active material in the cathode. In one example, the proportion of nitride is at least 5% by weight of the active material in the cathode.

[0065] In examples where the cathode material includes boron oxide and boron nitride, the weight ratio of the boron oxide to the boron nitride in the cathode material may be between 5:95 and 95:5, between 10:90 and 90:10, between 20:80 and 80:20, between 30:70 and 70:30, between 40:60 and 60:40, or between 45:55 and 55:45. In particular examples, the ratio is about 50:50. In one example, the proportion of boron oxide is at least 5% by weight of the active material in the cathode. In one example, the proportion of boron nitride is at least 5% by weight of the active material in the cathode.

[0066] In one example, the cathode active material consists essentially of a combination of a main group element nitride and a Group 1-13 element chalcogenide.

[0067] In one example, the cathode material includes nanostructures or mesostructures to provide increased surface area and improved contact with the electrolyte, for example, the nanostructures and mesostructures can include nanopores and / or mesopores.

[0068] In one example, the main group element nitride may have a grain size between 0.5 nm and 100 μm.

[0069] In one example, the oxide may have a particle size between 0.5 nm and 100 μm.

[0070] In one example, the cathode material includes a binder. The binder can be a non-conductive material such as a polymer. Those skilled in the art will readily understand that the binder is used to aid in the preparation of the cathode and to help the cathode adhere to a current collector when assembled into a battery. Suitable binders for use in cathodes will be understood by those skilled in the art. Preferably, the binder is selected from polyvinyl fluoride (PVDF) and polytetrafluoroethylene (PTFE).

[0071] In one example, the aluminum-ion battery cathode may include a conductive material selected from conductive carbon, acetylene black, and mixtures thereof. Those skilled in the art will appreciate that the conductive carbon is intended to counteract the decrease in conductivity caused by the addition of the binder.

[0072] In one example, the cathode comprises at least 75% (by weight) active material, or more preferably at least 80% (by weight) active material, or more preferably about 85% (by weight) active material.

[0073] In one example, the active material of a cathode of the present invention consists essentially of the oxides and / or nitrides identified herein. For example, in one embodiment of a cathode of the present invention, the active material consists essentially of an oxide of boron and a nitride of boron.

[0074] [battery] In another aspect of the invention, there is provided an aluminum-ion battery comprising a cathode as described herein, such as a cathode comprising a main group element nitride.

[0075] [anode] In one example, the aluminum-ion battery further includes an anode, such as an aluminum anode.

[0076] In one example, the anode may include at least one compound or material that can function as an anode in a battery, for example, the anode may include a material suitable for use with an electrolyte and with the cathode of the aluminum-ion battery.

[0077] The aluminum anode may comprise at least one material capable of undergoing a process selected from (i) intercalation, and (ii) reversible electrochemical deposition and dissolution at the intended operating temperatures of a battery according to the invention.

[0078] Suitable materials for use as the anode in the aluminum-ion batteries described herein will be readily apparent to those skilled in the art. However, for the avoidance of doubt, suitable materials for the anode include aluminum foil, e.g., aluminum sheet, a thin aluminum metal disk, and an aluminum alloy. In one example, the anode is an aluminum disk. In one example, the aluminum disk has a thickness of about 0.1 mm and an aluminum purity of about 99%. Alternatively, suitable anodes include aluminum alloys containing aluminum and at least one selected from the group consisting of chromium, cobalt, copper, iron, lithium, magnesium, manganese, nickel, silicon, tin, titanium, tungsten, vanadium, zinc, and zirconium.

[0079] [Electrolyte] In one example, the aluminum-ion battery includes an electrolyte that provides an electrical connection between the cathode and the anode and facilitates the movement of ions between them during charging and discharging of the battery.

[0080] In one example, the electrolyte comprises at least one ion suitable for use in an aluminum ion battery. 3+ , Mg 2+ , Li + , Na + , K. + or a combination thereof.

[0081] In one example, the electrolyte is an ionic liquid. The ionic liquid may have properties and / or characteristics that make it suitable or adaptable for use in an ionic battery. For example, the ionic liquid may be selected for use with a particular anode / cathode pair. Beneficial properties of the electrolyte include preventing or reducing oxidation of the anode and / or preventing or reducing the production of by-products during charging and discharging of the battery in use. Such by-products include chlorine gas, and hydrogen gas when an aqueous electrolyte is used.

[0082] In other preferred embodiments, the ionic liquid can be any ionic liquid that can act as a Lewis acid. Those skilled in the art will readily appreciate that Lewis acid properties are beneficial because they (i) prevent or reduce the formation of an oxide layer (AlO) on the anode, (ii) prevent or reduce the formation of dendrites (which can puncture the separator and cause short circuits), and (ii) prevent or reduce the evolution of chlorine gas (which can be evolved when using aqueous electrolytes such as NaCl or KCl).

[0083] Suitable ionic liquids include those that can be safely used in aluminum-ion batteries and will be known to those skilled in the art. Suitable ionic liquids may include imidazolium ionic liquids (including ethylmethylimidazolium halides (such as chlorides, bromides, iodides, and mixtures thereof)), acetamide, urea, NaCl-AlCl, aqueous solutions of aluminum salts, and ionic liquids containing metal hydroxides, and mixtures thereof. In one example, the ionic liquid includes aluminum chloride and 1-ethylmethylimidazolium halide. In another example, the 1-ethylmethylimidazolium halide is selected from the group consisting of 1-ethylmethylimidazolium chloride, 1-ethylmethylimidazolium bromide, 1-ethylmethylimidazolium iodide, and mixtures thereof.

[0084] In a particular example, the ionic liquid may comprise a combination of aluminum chloride (AlCl) and 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl). More particularly, the ionic liquid may be aluminum chloride (AlCl) and 1-ethyl-3-methylimidazolium chloride in a ratio of between about 1:1 and about 1.5:1, for example, about 1.3:1.

[0085] It is anticipated that other electrolytes, including those containing different ions and in different concentration ranges, will be suitable for use with the present invention.

[0086] [Separator] In a further embodiment, the aluminum-ion battery includes an ion-permeable separator for separating the cathode and anode in the aluminum-ion battery.

[0087] Suitable separators are known to those skilled in the art and may be selected from the group including polymers such as PTFE (polytetrafluoroethylene), cellulose acetate, nitrocellulose, polysulfone, polyethersulfone, polyacrylonitrile, polyamide, polyimide, polyethylene, polyvinyl chloride (PVC), NAFION, nylon, ceramic, polyester, rubber, glass separators such as glass microfiber, glass mat, and mixtures and combinations thereof.

[0088] In one example, the separator is a mesh made of a non-conductive material, in one example, the separator is glass microfiber, and in another example, the separator is an ion-permeable membrane.

[0089] [Current collector] In further embodiments, the aluminum-ion battery may include one or more current collectors. In one example, current collectors are located on both the anode and cathode sides of the battery. The battery may include a current collector for the cathode and / or anode. The current collector may be a substrate to which the cathode is attached and, in use, facilitates the flow of electrons through an external electrical circuit during discharge (and possibly charging) of the battery. Examples of suitable current collectors include any material or combination of materials that can conduct electricity. The current collector may be a mesh / sheet / foil made of any metal, which does not react with the electrolyte. Preferably, the current collector is selected from molybdenum, nickel, and tungsten.

[0090] [cell] In a further aspect of the present invention, there is provided an aluminum-ion battery cell comprising a cathode as described herein.

[0091] In one example, the cell further comprises an anode comprising aluminum.

[0092] In one example, the cell further comprises an electrolyte.

[0093] In one example, the cell further comprises an ion-permeable separator.

[0094] In a further aspect of the present invention, there is provided an aluminum-ion battery cell comprising a cathode, the cathode comprising an oxide of boron and boron nitride, wherein the ratio of the oxide of boron to the boron nitride is between 5:95 and 95:5 (by weight).

[0095] [Battery module] In a further aspect of the present invention, an aluminum-ion battery module is provided comprising two or more aluminum-ion batteries, at least one of the aluminum-ion batteries comprising a cathode as described herein.

[0096] [Electrical Equipment] In a further aspect of the present invention there is provided an electrical device comprising an aluminium ion battery substantially as described herein.

[0097] [use] In a further aspect of the present invention, there is provided the use of a cathode as described herein in an aluminum ion battery.

[0098] In a further aspect of the present invention, there is provided the use of a main group element nitride in the manufacture of a cathode for an aluminum ion battery cell.

[0099] In a further aspect of the present invention, there is provided the use of a main group element chalcogenide in the manufacture of a cathode for an aluminum ion battery cell.

[0100] In a further aspect of the present invention, there is provided the use of a combination of a main group element nitride and a chalcogenide of an element of Groups 1 to 13 in the manufacture of a cathode for an aluminum ion battery cell.

[0101] In a further aspect of the present invention, there is provided the use of a combination of an oxide of boron and boron nitride in the manufacture of a cathode for an aluminum-ion battery cell, wherein the ratio of the oxide of boron to the boron nitride is between 5:95 and 95:5 (by weight).

[0102] According to another embodiment of the present invention, the aluminum-ion battery can be used in electrical devices such as pedelecs, electric vehicles, computers, portable electrical devices, phones, tablets, storage devices for the electrical grid, etc.

[0103] [Manufacturing method] In a further aspect of the present invention, there is provided a method for manufacturing a battery, the method comprising forming a cathode for an aluminum-ion battery cell, the cathode comprising a main group element nitride or a chalcogenide of a Group 1-13 element, or a combination thereof.

[0104] In a further aspect of the present invention, there is provided a method for making a cathode for an aluminum-ion battery, said method comprising forming the cathode using a main group element nitride or a chalcogenide of an element from Groups 1 to 13, or a combination thereof.

[0105] In yet another embodiment of the present invention, the method for manufacturing a cathode for an aluminum ion battery comprises: (i) preparing a slurry, said slurry comprising: a. nitrides of main group elements and / or chalcogenides of elements of groups 1 to 13; b. a polar solvent; c. optionally, a binder; d. optionally, a conductive material; in any order, (ii) applying the slurry to a current collecting material; (iii) drying the slurry to provide a dry product; Includes:

[0106] The dry product preferably comprises at least 75% (by weight) active material, or more preferably at least 80% (by weight) active material, or more preferably about 85% (by weight) active material.

[0107] The polar solvent may be selected from water, ethanol, methanol, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), and N-methyl-pyrrolidone (NMP). In a preferred embodiment, the solvent is N-methyl-2-pyrrolidone (NMP).

[0108] The foregoing discussion should not be construed as limiting the scope of the present invention. It is anticipated that other electrolytes, including those containing different ions and in different concentration ranges, will be suitable for use with the present invention.

[0109] It should also be understood that batteries according to the present invention may include other components necessary to ensure desired performance. Representative additional components that may be included in batteries are described herein, but it should be understood that these are in non-limiting terms.

[0110] Although further embodiments of the invention, which should be considered in all its novel embodiments, will become apparent to those skilled in the art upon reading the following description, the following description provides at least one example of a practical application of the invention.

[0111] One or more embodiments of the present invention are described below, by way of example only and not by way of limitation, with reference to the following drawings:

[0112] [Definition] "Main group elements" refers to elements in Groups 1 and 2 (S block) and Groups 13 to 17 (P block excluding rare gases) of the periodic table. "Group 13 elements" means boron, aluminum, gallium, indium, and tellurium. "Chalcogenides" means oxides, sulfides, selenides, and tellurides. "Active material" with respect to the cathode material in a cell means the material in the cathode that reacts to, in part, generate an electromotive force during discharge of the cell.

[0113] [Detailed explanation] Aluminum-ion batteries are a promising alternative to other ion batteries, such as lithium-ion batteries. The present invention relates to a cathode for use in aluminum-ion batteries. Ion batteries operate using a reversible electrochemical deposition and dissolution process. During discharge of an ion battery, ions can be inserted into the gap between the layers of material forming the cathode, and electrons flow from the anode to the cathode to provide an EMF (electromotive force) and drive a load. This process is reversed during charging of the battery; i.e., ions are removed from the gap between the layers of material forming the cathode, and electrons flow from the cathode to the anode.

[0114] The present inventors have surprisingly found that nitride compounds of main group elements exhibit unexpectedly good activity as cathode active materials for and when used in aluminum ion batteries.

[0115] The present inventors have surprisingly found that boron oxide compounds, and in particular boric anhydride, exhibit unexpectedly good activity as cathode active materials for and when used in aluminum ion batteries.

[0116] The inventors have further surprisingly found that combinations of main group nitride compounds and Group 1-13 oxides exhibit unexpectedly good activity as cathode active materials for and when used in aluminum ion batteries.

[0117] In particular, the inventors have surprisingly found that a combination of boron nitride and an oxide of boron exhibits unexpectedly good activity as a cathode active material for and when used in an aluminum ion battery. Furthermore, the inventors have surprisingly found that a combination of hexagonal boron nitride and boric anhydride exhibits unexpectedly good activity as a cathode active material for and when used in an aluminum ion battery.

[0118] Reference is made to Figures 1 and 2, which are representative schematic diagrams of a battery (100) according to one embodiment of the present invention. The battery (100) is an aluminum-ion battery having a cathode (102) and an anode (104), which are disposed within a housing (106). The housing (106) may be any suitable housing for use in a battery, as would be readily understood by one skilled in the art. For example, suitable housings may include, but are not limited to, coin cells, pouch cells, cylindrical cells, and prismatic cells. An electrolyte (108) in the form of an ionic liquid is provided within the housing (106) and provides electrical connection between the cathode (102) and the anode (104) when the battery (100) is being charged or discharged.

[0119] The battery 100 also includes a separator 110 that is structured and / or arranged to prevent the anode and cathode from directly contacting each other. The separator 110 is preferably glass microfiber that is mounted in the housing 106. However, those skilled in the art will understand that any material or structure that is electrically insulating and prevents the cathode and anode from contacting each other can be used.

[0120] The cathode 102 and anode 104 each have terminals, designated 120 and 120', respectively. Terminals 120 and 120' (FIG. 2), such as molybdenum rods, facilitate attachment of the battery to an external load or charging device.

[0121] Further embodiments of battery 100 will become apparent from the following description of its specific components.

[0122] 3-5 and 23(b), an aluminum-ion battery cell (cell 4 in Table 1) containing a cathode with an active material consisting of a 1:1 ratio of boric anhydride and hexagonal boron nitride was prepared according to the method described in the Examples. Cycling of the cell at 50 mA / g showed a specific capacity near 220 mAh / g at a current density of 50 mA / g, and stabilized between about 10 and 25 mAh / g at current densities between 500 and 1500 mA / g.

[0123] 6 and 7, an aluminum-ion battery cell (cell 10 in Table 1) containing a cathode with an active material consisting of a 1:1 ratio of boric anhydride and carbon nitride CN was prepared according to the method described in the Examples. Cycling of the cell at 50 mA / g showed that the coulombic efficiency stabilized at approximately 100% and the specific capacity was near 90-120 mAh / g at a current density of 50 mA / g, and stabilized between about 10-30 mAh / g at current densities of 500-1500 mA / g.

[0124] 8 and 9, an aluminum-ion battery cell (cell 11 in Table 1) containing a cathode with an active material consisting of a 1:1 ratio of boric anhydride and aluminum nitride AlN was prepared according to the method described in the Examples. Cycling of the cell at 50 mA / g showed a specific capacity near 32-34 mAh / g at a current density of 50 mA / g, and stabilized at about 15-20 mAh / g at current densities of about 500-1500 mA / g.

[0125] 10 and 11, an aluminum-ion battery cell (cell 12 in Table 1) containing a cathode with an active material consisting of a 1:1 ratio of boric anhydride and silicon nitride Si3N4 was prepared according to the method described in the Examples. Cycling of the cell at 50 mA / g showed that the coulombic efficiency stabilized at approximately 100% and the specific capacity was near 25-28 mAh / g at a current density of 50 mA / g, and stabilized at about 10-20 mAh / g at current densities of 500-1500 mA / g.

[0126] 12 and 13, an aluminum-ion battery cell (cell 13 in Table 1) containing a cathode with an active material consisting of a 1:1 ratio of manganese oxide (MnO) and hexagonal boron nitride was prepared according to the method described in the Examples. Cycling of the cell at 50 mA / g showed that the coulombic efficiency stabilized at approximately 100% and the specific capacity was near 27-29 mAh / g at a current density of 50 mA / g, and stabilized at about 10-20 mAh / g at current densities of 500-1500 mA / g.

[0127] 14 and 15, an aluminum-ion battery cell (cell 14 in Table 1) containing a cathode with an active material consisting of a 1:1 ratio of manganese oxide (MnO) and carbon nitride CN was prepared according to the method described in the Examples. Cycling of the cell at 50 mA / g showed that the coulombic efficiency stabilized at approximately 100% and the specific capacity was near 30 mAh / g at a current density of 50 mA / g, and stabilized at about 10-20 mAh / g at current densities between 500 and 1500 mA / g.

[0128] 16 and 17, an aluminum-ion battery cell (cell 15 in Table 1) containing a cathode with an active material consisting of manganese oxide (MnO) and silicon nitride (SiN) in a 1:1 ratio was prepared according to the method described in the Examples. Cycling of the cell at 50 mA / g showed that the coulombic efficiency stabilized at approximately 100% and the specific capacity was near 40-55 mAh / g at a current density of 50 mA / g, and stabilized at about 10-20 mAh / g at a current density of 500-1500 mA / g.

[0129] 18 and 19, an aluminum-ion battery cell (cell 16 in Table 1) containing a cathode with an active material consisting of a 1:1 ratio of titanium dioxide (TiO) and hexagonal boron nitride was prepared according to the method described in the Examples. Cycling of the cell at 50 mA / g showed that the coulombic efficiency stabilized at approximately 100% and the specific capacity was near 60 mAh / g at a current density of 50 mA / g, and stabilized at about 20-30 mAh / g at current densities between 500 and 1500 mA / g.

[0130] 20 and 21, an aluminum-ion battery cell (cell 17 in Table 1) containing a cathode with an active material consisting of titanium dioxide (TiO) and carbon nitride (CN) in a 1:1 ratio was prepared according to the method described in the Examples. Cycling of the cell at 50 mA / g showed that at a current density of 50 mA / g, the coulombic efficiency stabilized at approximately 100% and the specific capacity was near 40-55 mAh / g, decreasing to about 10-15 mAh / g over cycling.

[0131] 22, aluminum-ion battery cells containing cathodes with boric anhydride and hexagonal boron nitride active material were prepared according to the methods described in the Examples. The proportion of boric anhydride varied between 75% and 100% of the active material in the cathode (Cells 5-9 in Table 1). Referring to Table 1, Cells 5-9 exhibited cell potentials of approximately 0.6-0.7 V, and the specific capacities (measured at 50 mA / g) tended to stabilize between 40-60 mAh / g.

[0132] 23(a), an aluminum-ion battery cell (Cell 1 in Table 1) containing a cathode with an active material consisting of 100% boric anhydride was prepared according to the method described in the Examples. Cycling of the cell at 50 mA / g showed that at a current density of 50 mA / g, the coulombic efficiency stabilized at approximately 90-100%, the specific capacity stabilized near 100-150 mAh / g, and the coulombic efficiency was between 80-85%.

[0133] 24 and 25, an aluminum-ion battery cell (cell 3 in Table 1) containing a cathode with an active material consisting of boric anhydride and hexagonal boron nitride in a 5:95 ratio (by weight) was prepared according to the method described in the Examples. Cycling of the cell at a current density of 50 mA / g showed that the specific capacity stabilized near 30 mAh / g, and between 5 and 10 mAh / g at current densities between 500 and 1500 mA / g.

[0134] 26 and 27, an aluminum-ion battery cell (cell 2 in Table 1) containing a cathode with an active material consisting of 100% hexagonal boron nitride was prepared according to the method described in the Examples. Cycling of the cell at 50 mA / g and 500 mA / g shows that the coulombic efficiency stabilizes at approximately 90-100% and the specific capacity stabilizes near 20 mAh / g at a current density of 50 mA / g, and is about 5-10 mAh / g at a current density of 500 mA / g. [Example]

[0135] Example 1: Cathode production Typically, a slurry containing 85% w / w active material is prepared by combining and mixing 6% binder and 9% conductive material in a solvent at room temperature. The slurry is sonicated and continuously stirred to form a homogeneous mixture and then doctor blade coated onto a current collector. The slurry is dried at room temperature and then dried under vacuum at 120°C for 12 hours to evaporate residual solvent. Discs are cut from this dried sheet and used as cathodes in laboratory battery test cells.

[0136] Example 2: Preparation of hexagonal boron nitride / boron oxide cathode material A 1:1 hexagonal boron nitride (hBN) / boric anhydride cathode was prepared as follows: A slurry containing a 1:1 mixture (by weight) of boric anhydride and boron nitride (85 wt%), polyvinyldiethylene fluoride (PVDF) binder (9 wt%), and conductive carbon (6 wt%) was prepared in N-methylpyrrolidone. The slurry was doctor blade coated onto molybdenum foil (0.1 mm thick, MTI Corporation) and dried in a vacuum oven at 120°C for 12 hours to adhere the slurry to the conductive substrate and evaporate the solvent. The specific loading of the hBN and boric anhydride active material was approximately 12 mg / cm. 2 It was.

[0137] Following the procedure above, hBN / boric anhydride cathodes with 5%, 75%, 80%, 85%, 90%, 95%, and 100% boric anhydride were prepared.

[0138] Example 3: Preparation of cathode materials containing other oxide / nitride combinations Cathode materials containing combinations of oxides and nitrides listed in Table 1 were prepared according to the methods described in Examples 1 and 2.

[0139] Example 4: Electrolyte The electrolyte was prepared as follows: Anhydrous aluminum trichloride, AlCl (Sigma-Aldrich), and 1-ethyl-3-methylimidazolium chloride, EMImCl (97%, Sigma-Aldrich) were mixed in a 1.3:1 molar ratio at room temperature under inert conditions.

[0140] Example 5: Cells A polyether ether ketone (PEEK) pouch cell was prepared as follows: Under inert conditions, a cathode was positioned at the bottom of the PEEK cell. A glass microfiber (grade GF / F, Whatman) separator was positioned in the cell. 80 μl of the electrolyte from Example 4 was added to wet the separator. Aluminum foil (thickness: 0.1 mm, 99%, GoodFellow) was used as the anode and placed on top of the separator. The cell was then sealed to prevent air or moisture from entering the cell.

[0141] Cells were prepared with cathodes having the active materials (oxide and nitride components) specified in Table 1, with each cathode prepared according to the general procedure described in Example 2. Testing was performed using a Neware® Battery Analyzer, BTS3000. Test parameters included current densities of 50, 500, 1000, or 1500 mA / g between voltages of 0.02 and 2.35 V. Each cell was cycled 50 times at each current density.

[0142] [Table 1]

[0143] Unless the context clearly requires otherwise, throughout the specification and claims, the terms "comprise, compris- ing, etc., " are to be interpreted in an inclusive sense in the sense of "including, but not limited to," as opposed to an exclusive sense.

[0144] Reference to a numerical range disclosed herein (e.g., 1 to 10) also incorporates reference to every reasonable number within that range (e.g., 1, 1.1, 2, 3, 3.9, 4, 5, 6, 6.5, 7, 8, 9, and 10), and also incorporates every range of reasonable numbers within that range (e.g., 2 to 8, 1.5 to 5.5, and 3.1 to 4.7), and therefore, all subranges of all ranges expressly disclosed herein are also intended to be expressly disclosed. These are merely examples of what is specifically intended, and all possible combinations of numerical values ​​between the lowest and highest values ​​recited are also considered to be expressly set forth in this application.

[0145] The entire disclosures of all applications, patents and publications, cited above and below, if any, are hereby incorporated by reference.

[0146] Reference to prior art in this specification is not, and should not be taken as, an acknowledgment or any form of suggestion that the prior art forms part of the common general knowledge in the field of endeavor in any country throughout the world.

[0147] The invention may also be said to reside generally in any or all combinations of two or more of the parts, elements, features referenced or indicated in the specification of this application, individually or collectively, such parts, elements, features.

[0148] Where reference has been made in the above description to components having integers or their known equivalents, those integers are incorporated herein as if individually set forth.

[0149] It should be noted that various changes and modifications to the presently preferred embodiments described herein will become apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the present invention and without diminishing its attendant advantages. Accordingly, such changes and modifications are intended to be embraced by the present invention.

[0150] [reference] ·Lin,Meng-Chang;Gong,Ming;Lu,Bingan;Wu,Yingpeng;Wang,Di-Yan;Guan,Mingyun;Angell,Michael;Chen,Changxin;Yang,Jiang;Hwang,Bing-Joe;Dai,Hongjie(6 April 2015).”An ultrafast rechargeable aluminum-ion battery”.Nature.520:324-328.doi:10.1038 / nature14340.PMID25849777. ·Das,Shyamal K.;Mahapatra,Sadhan;Lahan,Homen(2017).”Aluminum-ion batteries:developments and challenges”.Journal of Materials Chemistry A:6347-6367.doi:10.1039 / c7ta00228a. ·Ambroz,F.;Macdonald,TJ;Nann,T.Trends in Aluminum-Based Intercalation Batteries.Adv.Energy Mater.2017,1602093. ·Zafar,ZAet al.A super-long life rechargeable aluminum battery.Solid State Ion.320,70-75(2018). ·Eftekhari,A.Low voltage anode materials for lithium-ion batteries.Energy Storage Mater.7,157-180(2017). ·Mukherjee,R.&Koratkar,N.A.United States Patent No.9,819,220. ·Brown,G.M.et al.United States Patent No.9,997,802.

Claims

1. 1. A cathode for an aluminum-ion battery, the cathode comprising an active material, the active material comprising an oxide of boron.

2. 10. The cathode of claim 1, wherein the active material further comprises boron nitride.

3. 3. The cathode of claim 2, wherein the ratio of said oxide of boron to said boron nitride is between 5:95 and 95:5 (by weight).

4. 4. The cathode according to claim 2 or 3, characterized in that the ratio of the oxide of boron to the boron nitride is between 10:90 and 90:10, or between 20:80 and 80:20, or between 30:70 and 70:30, or between 40:60 and 60:40 (by weight).

5. 5. The cathode according to claim 1, wherein the oxide of boron accounts for at least 75% (by weight) of the active material.

6. 6. The cathode of claim 1, wherein the oxide of boron comprises boric anhydride.

7. A cathode according to any one of claims 2 to 4, characterized in that the boron nitride comprises a 2D layered material.

8. 8. The cathode according to claim 2, wherein the boron nitride comprises hexagonal boron nitride.

9. The cathode according to any one of claims 1 to 8, further comprising a conductive material.

10. 10. The cathode of claim 9, wherein the conductive material comprises conductive carbon.

11. 1. An aluminum-ion battery cell comprising a cathode, wherein the cathode comprises an oxide of boron and boron nitride, wherein the ratio of the oxide of boron to the boron nitride is between 5:95 and 95:5 (by weight).

12. 12. The cell of claim 11, wherein the ratio of the oxide of boron to the boron nitride is between 10:90 and 90:10, or between 20:80 and 80:20, or between 30:70 and 70:30, or between 40:60 and 60:40 (by weight).

13. 12. The cell of claim 11, wherein the ratio of said oxide of boron to said boron nitride is about 1:1 (by weight).

14. The cell of any one of claims 11 to 13, wherein the oxide of boron comprises boric anhydride.

15. The cell of any one of claims 11 to 14, characterized in that the boron nitride comprises a 2D layered material.

16. The cell of any one of claims 11 to 15, wherein the boron nitride comprises hexagonal boron nitride.

17. The cell of any one of claims 11 to 16, further comprising an anode, said anode comprising aluminium.

18. 18. The cell of claim 17, further comprising an electrolyte in electrical contact with the anode and / or cathode, and optionally an ion-permeable separator disposed between the anode and the cathode.

19. 1. Use of a combination of an oxide of boron and boron nitride in the manufacture of a cathode for an aluminum-ion battery cell, characterized in that the ratio of the oxide of boron to the boron nitride is between 5:95 and 95:5 (by weight).

20. 20. Use according to claim 19, characterized in that the ratio of the oxide of boron to the boron nitride is between 10:90 and 90:10, or between 20:80 and 80:20, or between 30:70 and 70:30, or between 40:60 and 60:40 (by weight).

21. 20. The use according to claim 19, characterized in that the ratio of the oxide of boron to the boron nitride is about 1:1 (by weight).

22. The use according to any one of claims 19 to 21, characterized in that the oxide of boron comprises boric anhydride.

23. Use according to any one of claims 19 to 22, characterized in that the boron nitride comprises a 2D layered material.

24. Use according to any one of claims 19 to 23, characterized in that the boron nitride comprises hexagonal boron nitride.

25. The use according to any one of claims 19 to 24, characterized in that the aluminium-ion battery cell further comprises an anode, the anode comprising aluminium.

26. 26. The use according to any one of claims 19 to 25, characterized in that the aluminium-ion battery cell further comprises an electrolyte in electrical contact with the anode and / or the cathode, and optionally an ion-permeable separator disposed between the anode and the cathode.

27. Use of a cathode according to any one of claims 1 to 10 in an aluminium ion battery.

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